Preparation of an allyl amine and quaternary diallyl ammonium compounds therefrom

ABSTRACT

An allyl amine compound such as an allyl dialkyl amine is prepared by the reaction of ammonia or a water soluble amine with an allyl halide in the presence of an alkali metal or alkaline earth metal hydroxide or carbonate using a two-phase reaction system comprising water and a water-immiscible organic liquid. The allyl amine product is of an exceptionally high purity and contains relatively small amounts of salts. When the reaction method is employed to prepare an allyl dialkyl amine, the allyl dialkyl amine can effectively be quaternized to prepare a pure diallyl dialkyl ammonium compound at high yields.

The present invention relates to a method for preparing an allyl aminecompound and to a method for preparing a quaternary, diallyl ammoniumcompound therefrom.

Quaternary diallyl dialkyl ammonium compounds such as diallyl dimethylammonium chloride are monomeric materials which can be polymerized, bothhomo- and copolymerized, to form polymers useful in a variety ofapplications. For example, a polymer derived, at least partially, from adiallyl dimethyl ammonium chloride can be employed as a flocculant inwaste water treatment, as a wet strength agent or retention and drainageaid in the preparation of paper, as an antistatic additive, an acid-dyereceptor or a biocide.

Heretofore, quaternary diallyl dialkyl ammonium compounds haveconventionally been prepared, on a commercial scale, by the reaction, inan aqueous medium, of a secondary amine such as dimethyl amine with anallyl halide (e.g., allyl chloride) in the presence of an alkali metalhydroxide (e.g., sodium hydroxide). See, for example, U.S. Pat. No.2,923,701. In general, an excess of the allyl halide is employed toensure complete reaction of the secondary amine. The excess allyl halideis stripped under vacuum. The resulting product is an aqueous solutioncontaining the desired quaternary diallyl dialkyl ammonium compound.Unfortunately, a large amount of salt (e.g., sodium chloride) is formedduring the reaction, and is present in the reaction product. Thisrestricts the ability to polymerize the resulting compound.

Various methods have been proposed to reduce the amount of salt andotherwise improve the purity of the quaternary ammonium product. See,for example, U.S. Pat. No. 3,472,740. Using the described techniques,the purity of the quaternary ammonium compound is improved whilesimultaneously reducing the amounts of salt in solution by evaporatingwater from the aqueous reaction product such as by steam distillation toremove the unreacted allyl chloride and secondary amine and toprecipitate the salt. The precipitated salt can subsequently be removedfrom the aqueous solution by filtration. Following evaporation of thewater and removal of the precipitated salt, the aqueous solution of thequaternary ammonium compound can be passed over an activated carbon tofurther purify the reaction product. Unfortunately, the amounts of waterwhich can be evaporated (and hence, the amounts of salt which can beprecipitated from solution) is limited due to the hygroscopic nature ofthe quaternary ammonium compound. In fact, upon the removal of allpossible water, a highly viscous oil of an over-saturated solution ofthe quaternary ammonium compound in water which still contains a highpercentage of salt is formed. Moreover, the described purificationmethod is time consuming and capital intensive.

Yet another means for reducing the amount of salt formed in thepreparation of the quaternary ammonium compound is disclosed in Japanesepatent specification 50-77308. Specifically, the disclosed methodcomprises precipitating the salt with organic solvent following thereaction of dialkyl amine with allyl halide. Subsequently, theprecipitated salt is removed to yield an aqueous solution of thequaternary ammonium compound. Unfortunately, the described method doesnot precipitate all the salt and the product still contains a relativelyhigh concentration of salt. Moreover, it is necessary using thedescribed process, to separate the added organic liquid from the mixtureof water and quaternary ammonium compound.

In addition to containing relatively large amounts of salt, using thedescribed techniques and other known techniques, the quaternary ammoniumcompound is prepared as a solution in an aqueous liquid. Therefore, itis necessary to ship large amounts of water in transporting thequaternary ammonium product. In addition, polymerization of thequaternary ammonium compound is limited to aqueous polymerizationsystems. Moreover, further improvements in yield of the desiredquaternary ammonium compound are desired.

The preparation of a solid diallyl dimethyl ammonium chloride has beendescribed in Belgian Patent No. 664,427. The described techniqueinvolves a two-step reaction process. In the first reaction step, allyldimethyl amine is prepared by reacting, in aqueous liquid, dimethylamine with allyl chloride in the presence of caustic soda. Followingthis reaction, an additional amount of caustic soda is added to thereaction mixture to separate the allyl dimethyl amine from the remainderof the reaction mixture. Specifically, upon the addition of excesscaustic soda, a two-phase system results. The upper phase comprises thedesired allyl dimethyl amine and up to and over 10 weight percent waterand the lower phase comprises sodium hydroxide, sodium chloride, theremainder of the water, up to and exceeding 5 percent dimethyl amine andsmall amounts of allyl dimethyl amine. Subsequently, the upper phase isseparated from the reaction mixture and dried over caustic soda pellets.The resulting material is distilled and the fraction boiling at 59° to62° C. collected. This fraction is then added, with freshly distilledallyl chloride, to freshly distilled acetone and reacted to form diallyldimethyl ammonium chloride in the form of crystals. Although theresulting solid diallyl dimethyl ammonium chloride is relatively pure ascompared to a similar product prepared in an aqueous solution using theone step reaction method of the prior art, the yield of dimethyl allylamine in the first reaction step is only 67.5 percent based on theamount of allyl chloride added. In addition, the water phase containssignificant amounts of the allyl dimethyl amine following the firstreaction step. Moreover, due to the fact that large amounts of water arepresent in the allyl dimethyl amine formed during the first reactionstep, the problems associated with water removal remain. Hence, theallyl dimethyl amine prepared in the first reaction step, it must bedried over caustic soda pellets to remove the water, a time consumingstep.

In view of the stated deficiencies of the prior art methods, it remainshighly desirable to provide a method for preparing, at a high yield andpurity, an allyl amine compound and a quaternary diallyl ammoniumcompound which method can suitably be employed in preparing the compoundas a solid.

Accordingly, in one aspect, the present invention is a method forpreparing an organic soluble allyl amine. The reaction method comprisesreacting, in a liquid reaction diluent, ammonia or a water soluble aminewith allyl halide in the presence of an alkali metal or alkaline earthmetal hydroxide or carbonate and is characterized by the fact that thereaction diluent comprises a two phase liquid system consisting of waterand water-immiscible organic liquid.

By preparing the allyl amine in a two-phase liquid system comprisingwater and a water-immiscible organic liquid, the disadvantages inherentin the prior art processes are eliminated. Specifically, the allyl aminecompound will remain, following its preparation, in the organic liquidphase. Alternatively, any salt as well as other impurities formed duringthe reaction will remain in the aqueous liquid phase. Moreover, theorganic liquid phase is essentially water-free or contains relativelylow amounts of water. Therefore, the resulting allyl amine does notrequire purification prior to its subsequent use. The allyl aminecompound is useful in the preparation of quaternary ammonium compounds,particularly quaternary, diallyl dialkyl ammonium compounds.

In a second aspect, the present invention is a method for preparing adiallyl dialkyl quaternary ammonium compound by sequentially reacting asecondary amine with allyl halide in a liquid reaction diluent and thepresence of an alkali metal or alkaline earth metal hydroxide orcarbonate and subsequently reacting the thus prepared allyl dialkylamine with additional amounts of an allyl halide in a liquid reactiondiluent to form a quaternary diallyl dialkyl ammonium salt, said methodbeing characterized by the fact that the reaction of the secondary amineand allyl halide is conducted in a two-phase reaction system comprisingan aqueous liquid and a water-immiscible organic solvent and at least aportion of the organic liquid phase is separated for further reaction ofthe allyl dialkyl amine contained by this organic phase to prepare thediallyl dialkyl quaternary ammonium compound.

Using the described two-step method, following the first reaction stepin which the allyl dialkyl amine is prepared, the organic phase containsthe allyl dialkyl amine and essentially no salt or water. Therefore,this phase can be separated from the aqueous phase and the allyl dialkylamine directly (i.e., without purification) reacted with additionalamounts of the allyl halide to form the quaternary, diallyl dialkylammonium compound. The quaternary diallyl dialkyl quaternary ammoniumformed is a solid material containing no significant amounts ofinorganic salt and surprisingly low amounts of other impurities.Therefore, it can readily be polymerized, both homo- and copolymerized,to form a high molecular weight polymer useful in a wide variety ofend-use applications.

In the practice of the present invention, the allyl amine compound isprepared from ammonia or an amine represented by the general structuralformula: ##STR1## wherein R₁ is hydrogen, an alkyl group, or a hydroxyalkyl group and R₂ is an alkyl or hydroxy alkyl group. Alternatively,the combination of R₁ and R₂ can form a cyclic ring such as representedby the following general formula: ##STR2## wherein each R₃ and R₄ areindividually (CR₅ H)_(p) --(CR₆ H)_(q) and each R₅ and R₆ areindependently hydrogen or an alkyl group (preferably methyl, ethyl orpropyl), p is an integer from 0 to 4 (preferably 1 or 2), q is aninteger from 0 to 4 (preferably 1 or 2), the sum of p and q is 1 to 4, Zis oxygen or sulfur and n is 0 or 1. R₁ is advantageously hydrogen or analkyl or hydroxyalkyl group and R₂ is an alkyl or hydroxyalkyl group.Preferably, the amine is a secondary amine wherein each R₁ and R₂ isindependently an alkyl group having from 1 to 12 carbon atoms or ahydroxyalkyl group having from 2 to 8 carbon atoms. More preferably, theamine is a secondary amine wherein each R₁ and R₂ is individuallymethyl, ethyl or hydroxy ethyl. Most preferably, each R₁ and R₂ isindependently methyl or ethyl.

The allyl halides employed in the practice of the present invention areadvantageously allyl halide, methallyl halide or ethallyl halide withthe halide preferably being chloride or bromide, most preferablychloride. Most preferably, allyl chloride is employed in the practice ofthe present invention.

The allyl amines are prepared by reacting ammonia or an amine with theallyl halide in the presence of an alkali metal or an alkaline earthmetal hydroxide or carbonate. Of these compounds, those advantageouslyemployed are the alkali metal hydroxides or carbonates with the alkalimetal hydroxides being preferred. Potassium hydroxide or sodiumhydroxide, particularly sodium hydroxide are most preferred.

The amounts of the amine, allyl halide and hydroxide or carbonate mostadvantageously employed in preparing the allyl amines are dependent on avariety of factors including the specific reactants employed and theconditions of reaction and can readily be determined by those skilled inthe art by simple experimentation. In general, the allyl amine isprepared using from 0.9 to 3 equivalents of amine for each equivalent ofallyl halide. It is generally preferable to use a stoichiometric excessof amine, with from more than 1 to 2.5 equivalents of amine preferablybeing employed for each equivalent of allyl halide. The hydroxide orcarbonate is advantageously employed in an amount sufficient tocompletely neutralize the hydrochloric acid formed by the reaction ofthe allyl halide with amine, but large amounts of the hydroxide orcarbonate are generally not preferred. When employing the preferredalkali metal hydroxide, the hydroxide is advantageously employed in anamount from 0.9 to 5 moles per mole of the allyl halide.

In a preferred embodiment of this invention wherein the allyl amine isprepared by reacting a secondary amine and an allyl halide in thepresence of an alkali metal hydroxide, the molar ratio of the secondaryamine:allyl halide:alkali metal hydroxide is advantageously1:0.5-1.2:0.98-2, with molar ratios of 1:0.8-1.05:1.0-1.1 beingpreferred.

In the practice of the present invention, the allyl halide, amine andhydroxide or carbonate are mixed in a two-phase reaction systemcomprising water and a water-immiscible organic liquid and reacted atconditions sufficient to form the desired allyl dialkyl amine. By theterm "water-immiscible organic liquid", it is meant an organic liquidwhich, at the reaction conditions employed, cannot uniformly be mixed orblended with water to form a single liquid phase. Preferably, less than5 weight percent water is capable of being dissolved in the specificorganic liquid employed at 20° C. and 760 mmHg. Preferably, at 20° C.and 760 mmHg, the organic liquid contains less than 1, more preferablyless than 0.5, most preferably less than 0.25 weight percent ofdissolved water.

Representative organic liquids which are suitably employed in thepractice of the present invention include aromatic hydrocarbons such astoluene, benzene, m-, o-, and p-xylenes, mesitylene, ethylbenzene andcumene; chlorinated hydrocarbons such as trichloroethylene,tetrachlorocarbon, methylene chloride and perchloroethylene; aliphatichydrocarbons having 6 or more carbon atoms such as hexane, heptane,cyclohexane; petroleum ethers; and lower dialkyl ethers such asdiethylether, diisopropyl ether or ethyl propyl ether. Compatiblemixtures of two or more of the specified organic liquids can beemployed.

Preferably, the organic liquid employed is an aromatic hydrocarbon,particularly benzene or toluene and various chlorinated hydrocarbons,particularly trichloroethylene. More preferably, the organic liquid isan aromatic hydrocarbon, with toluene and benzene, particularly toluene,being most preferred.

The term "water" is meant to include tap water, deionized water oraqueous solutions.

The amounts of water and the organic liquid most advantageously employedin the practice of the present invention are dependent on variousfactors, including the specific organic liquid and reactants,particularly the amine and hydroxide or carbonate, employed and theconditions at which the reaction is conducted. Although not absolutelynecessary, water is generally advantageously employed in an amountsufficient to dissolve the entire amounts of salt prepared duringreaction as well as the amine and hydroxide or carbonate employed. Ingeneral, however, large excesses of water are to be avoided. Preferably,the reaction mixture will contain from 40 to 250 weight percent waterbased on the total weight of the amine and hydroxide or carbonateemployed. The amounts of organic liquid employed are not narrowlycritical to the practice of the present invention provided sufficientamounts are employed to dissolve the allyl amine product. The organicliquid can be employed in amounts from 10 to 1000 or more volume percentbased on the total volume of allyl halide employed. However, it isgenerally preferable, for purposes of economics, to employ the organicliquid in an amount such that the organic phase will contain from 30 to60 percent, by weight, of the allyl amine reaction product.

Although the relative concentration of the aqueous liquid phase toorganic liquid phase is not particularly critical to the practice of thepresent invention, in general, the volume ratio of organic phase:aqueousphase is advantageously from as low as 0.05:1 to as high as 25:1. Theratio of the volume of organic phase:aqueous phase is preferably from0.1:1 to 10:1, with a volume ratio of from 0.5:1 to 2:1 being morepreferred.

The method of the present invention will now be described withparticular reference to the preparation of an allyl dialkyl amine byreacting a secondary amine with an allyl halide in the presence of analkali metal hydroxide. However, it is easily extended to include theproduction of other allyl amines using different amines, allyl halidesand hydroxides or carbonates.

In preparing the allyl dialkyl amine, the alkyl halide and alkali metalhydroxide are preferably added, in a controlled manner over a period oftime, to a mixture of the water, organic liquid and secondary amine. Bythe controlled addition of the allyl halide and alkali metal hydroxide,the secondary amine is present at high concentrations, in comparison tothe concentration of the allyl halide and alkali metal hydroxide, whichsuppresses the formation of a water-soluble diallyl dialkyl ammoniumsalt as well as by-products related thereto reduced.

The temperatures most advantageously employed in reacting the allylhalide with the secondary amine are dependent on the specific reactantsemployed, the type and concentration of the organic liquid employed, therelative ratio of the organic phase to the aqueous phase and the desiredyields and product properties. In general, the maximum temperatureemployed is limited by the formation of excessive by-products which tendto color the reaction product whereas the lower temperatures of reactionare limited by the desired rate of reaction. In general, the reaction isconducted at a temperature from 15° to 70° C., with temperatures from20° to 60° C. being more preferred. The reaction mixture isadvantageously maintained at these temperatures for a period of from 2to 10 hours, more preferably from 5 to 9 hours.

During the addition of the alkali metal hydroxide and allyl halide tothe reaction mixture and subsequent reaction of the secondary amine withthe allyl halide, the reaction mixture is advantageously agitated.

Upon completion of the reaction, the thus prepared allyl amine compoundis contained in the organic phase (i.e., is dissolved in the organicliquid). In addition to the desired reaction product, the organic phasemay contain small amounts of unreacted secondary amine and allyl halide.Alternatively, the aqueous phase will contain alkali metal halide (e.g.,sodium chloride) unreacted secondary amine and impurities. The organicand aqueous phases are then separated and the thus prepared allyl aminecompound can be used without subsequent purification.

In a preferred embodiment of the present invention, the allyl aminecompound which is prepared is an allyl dialkyl amine and this reactionproduct is quaternized to form a quaternary ammonium compound. Inconducting the quaternization reaction, the allyl dialkyl amine andallyl halide are advantageously mixed in a liquid reaction diluent atconditions sufficient to quaternize the allyl dialkyl amine. In onemethod for preparing the quaternary, diallyl dialkyl ammonium compoundfrom the allyl dialkyl amine, quaternization can be conducted by addingallyl halide directly to the separated organic phase containing theallyl dialkyl amine. Alternatively, the allyl dialkyl amine product canbe recovered at an exceptional purity from the separated organic liquidphase and, following separation, the allyl dialkyl amine redissolved inthe same or different liquid for subsequent quaternization to thedesired diallyl dialkyl ammonium compound.

Preferably, the quaternary ammonium compound being prepared is insolublein the liquid employed as the reaction diluent in the quaternizationreaction. Specifically, although various polar solvents such as dimethylsulfoxide, dimethyl formamide, acetonitrile, water or a mixture of waterand a water-immiscible organic liquid can be employed as the reactiondiluent for the quaternization reaction, the resulting quaternaryammonium compound is generally soluble in these liquids making recoveryof the product, in the solid form, difficult. Advantageously, thequaternization of the allyl dialkyl amine to a diallyl dialkyl ammoniumcompound is conducted in an essentially water-free reaction medium dueto the fact that the presence of water in the quaternization reactionmixture will result in the formation of some oily, non-crystallinematerial.

The organic liquids which can be employed in preparing the allyl dialkylamine can also generally be employed in the quaternization reaction. Inaddition, other organic liquids which do not possess the necessaryimmiscibility in water which is required for the preparation of theallyl dialkyl amine using the method of the present invention are alsosuitably employed as the reaction diluent in the quaternization step.For example, in addition to those organic liquids which can be employedin preparing the allyl dialkyl amine, lower ketones such as acetone,methyl ethyl ketone and acetophenone can advantageously be employed asthe reaction diluent in the quaternization reaction. The preferredorganic liquid for use as the quaternization reaction diluent includethe lower ketones, particularly acetone; the aromatic hydrocarbons andchlorinated hydrocarbons. Most preferably, quaternization is conductedin a lower ketone, with acetone being most preferred.

The rate of the quaternization reaction as well as the nature and purityof the quaternary ammonium compound prepared during the quaternizationare influenced by the amounts and specific reactants and organic liquidreaction diluent employed. In general, to obtain a product of desiredpurity, the organic liquid reaction diluent is advantageously employedsuch that the reaction mixture advantageously contains at least twovolumes of the organic liquid for each volume of the allyl dialkyl amineto be quaternized. Preferably, from 2 to 50 volumes of the organicliquid reaction diluent are employed for each volume of the amine to bequaternized. More preferably, from 2 to 5 volumes of the organic liquidreaction diluent are employed for each volume of the allyl dialkylamine.

The allyl halide is employed in at least a stoichiometric amount.Preferably, to avoid significantly long reaction times, the allyl halideis employed in an amount of at least 1.5 moles for each mole of theallyl dialkyl amine to be quaternized. More preferably, from 1.5 to 6,most preferably from 2 to 3, moles of the allyl halide are employed foreach mole of the allyl dialkyl amine to be quaternized.

Using these amounts of allyl halide, the quaternization reaction isadvantageously conducted at temperatures from 20° to 60° C., preferablyfrom 30° to 45° C. At these temperatures, the quaternization reaction isgenerally conducted for periods of from 6 to 15 hours.

Using a sufficiently non-polar solvent, following the quaternization ofthe allyl dialkyl amine, the resulting quaternary diallyl dialkylammonium compound will precipitate from solution. The quaternaryammonium compound can therefore be recovered using conventionalfiltration techniques. Prior to subsequent use, the filtered product isthen dried to form a solid, quaternary diallyl dialkyl ammoniumcompound. The resulting solid crystal, although containing traces of theorganic solvent, is of relatively high purity and contains essentiallyno alkali metal halide. Therefore, it can easily be polymerized to highmolecular weights in both aqueous and non-aqueous systems. Since theresulting polymer contains no salt, it can be employed in a wide varietyof applications to which polymers containing higher concentrations ofsalt cannot be employed.

The following examples are set forth to illustrate this invention andshould not be construed to limit its scope. All percentages and parts inthe examples are by weight unless otherwise indicated.

EXAMPLE 1

A. Preparation of an Allyl Dimethyl Amine

To a suitably sized flask equipped with a thermometer, agitator, refluxcondensor operating at a temperature of -45° C. and heating and coolingmeans was added 1240 milliliters (ml) of a 40 percent aqueous solutionof dimethyl amine and 1000 ml parts cf toluene. During this addition,the temperature of the vessel was maintained at 25° C. While agitatingthe dimethyl amine/water/toluene mixture, a first stream of a solutionof 41 grams. (gm) of sodium hydroxide, 60 ml of water and a secondstream of 820 ml of allyl chloride were simultaneously added dropwise tothe flask over a period of 5 hours. Following complete addition of thesodium hydroxide and allyl chloride, the reaction mixture comprised amolar ratio of dimethyl amine:allyl chloride:sodium hydroxide of1:1:1.05. During the addition of the allyl chloride and sodiumhydroxide, the temperature of the reaction mixture rose. It wasmaintained at 40° C. during the addition and subsequently slowlyincreased to 70° C. At this temperature, the reaction mixture wasmaintained under a slight reflux. The temperature was maintained at 70°C. for 3 hours (total reaction time was 8 hours) after complete additionof the allyl chloride and sodium hydroxide. The reaction mixture wasthen cooled to 25° C. and agitation stopped. Upon ceasing agitation, thetoluene phase which contained allyl dimethyl amine rose to the top ofthe reaction vessel and the aqueous phase which contained the sodiumchloride salt sank to the bottom of the reaction vessel. The toluenephase was separated from the aqueous phase of the reaction vessel. Uponanalysis of the organic phase, it was found that the yield of allyldimethyl amine was over 90 percent based on the amounts of allylchloride employed.

B. Quaternization in Toluene

The thus prepared allyl dimethyl amine was quaternized withoutsubsequent separation or purification by deleting a portion of theresulting solution of allyl dimethyl amine with additional toluene toform a 35 percent solution. One hundred grams of this solution wereplaced in a suitable reaction vessel and 200 ml of allyl chloride addedthereto at room temperature. The resulting mixture was heated to atemperature of 35° C. for a period of 8 hours. At this time, the diallyldimethyl ammonium chloride product (with essentially completeconversion) had precipitated from solution and was filtered, washed withwater-free toluene and dried under vacuum. The resulting solid crystalsof the diallyl dimethyl ammonium chloride were extremely pure,containing essentially no (i.e., less than 100 parts of sodium chlorideper million parts (ppm) of the quaternary ammonium compound) sodiumchloride and could effectively be employed for subsequentpolymerization.

C. Quaternization in Acetone/Toluene

A second portion of the allyl dimethyl amine was quaternized by adding150 gm of the solution of the allyl dimethyl amine in toluene to 500 mlacetone containing 58 ml of allyl chloride. The solution was heated to atemperature of 40° C. for a period of 24 hours. The diallyl dimethylammonium chloride formed by the quaternization reaction precipitatedfrom solution in long, uncolored needles. Conversion was greater than 95percent. The needles were recovered using conventional filtrationtechniques and dried under vacuum. The filtered needles were found to bepure and to contain essentially no sodium chloride and couldsubsequently effectively polymerize.

When the same quaternization was repeated except using reactiontemperatures of 25° C., a product of similar purity was prepared exceptthat the quaternization reaction required two days.

D. Quaternization in Acetone

A third portion of the toluene solution containing the allyl dimethylamine was fractionated. The fraction boiling at 61° to 63° C. wascollected. Sixty grams of this fraction were added to 136 gm acetonecontaining 156 gm of allyl chloride. The mixture was maintained at atemperature of 35° C. for a period of 8 hours at which time there wasgreater than 95 percent conversion. The quaternary ammonium compoundprecipitated in long, uncolored needles from solution. The needles wererecovered using conventional filtration techniques and found to be of anextremely high purity. Specifically, the diallyl dimethyl ammoniumchloride product contained less than 2 ppm acetone, less than 0.7 ppmdimethyl amine, less than 0.4 ppm of unreacted allyl dimethyl amine, 20ppm of allyl dimethyl amine.HCl and less than 40 ppm of sodium chloride.Comparatively, the diallyl dimethyl ammonium chloride prepared by themethods of the prior art contain at least 1 percent (10,000 ppm) sodiumchloride.

E. Quaternization in Trichloroethylene

Another portion of the allyl dimethyl amine was fractionated and thefraction of the product boiling at 61° to 63° C. recovered. One hundredgrams of the resulting fraction were added to 500 gm oftrichloroethylene. Subsequently, 270 gm of allylchloride were added tothe mixture. The temperature of the reaction mixture was maintained at35° C. for 8 hours. The reaction mixture was continuously agitatedduring addition of allylchloride and thereafter. At this time, needlesof dimethyl dialkyl ammonium chloride floated in a thick layer on thesurface of the solution. The needles were filtered and dried usingconventional techniques. They are of extremely high purity and containless than 4 ppm trichloroethylene, less than 60 ppm of amines and lessthan 40 ppm sodium chloride.

F. Quaternization in the presence of Water

Yet another portion of the toluene solution of allyl dimethyl amine wasquaternized by placing 150 gm of the allyl dimethyl amine solution and17.1 ml of allyl chloride in 200 ml water. The resulting mixture formeda two-phase system, i.e., a toluene phase containing the allyl dimethylamine and allyl chloride and an aqueous phase. The two-phase system wasagitated and the temperature increased to 40° C. This temperature wasmaintained for 8 hours, at which time essentially complete conversion ofthe allyl dimethyl amine to diallyl dimethyl ammonium chloride had takenplace. The diallyl dimethyl ammonium chloride was contained in theaqueous phase. The toluene phase which contained the excess allylchloride was separated from the aqueous phase which contained, insolution, the diallyl dimethyl ammonium chloride. To remove anyremaining toluene and volatile impurities from the aqueous phase, it wassubjected to a stripping operation for three hours at 40° C. and apressure of 150 mmHg. Following the stripping operation, the aqueoussolution comprised 60 percent, by weight, of the diallyl dimethylammonium chloride and essentially no sodium chloride. The resultingdiallyl dimethyl ammonium chloride was effectively polymerized usingconventional techniques.

G. Quaternization in a Highly Polar Solvent

Another portion of the allyl dimethyl amine in toluene was fractionedand the fraction boiling at 61° to 63° C. collected. Sixty grams of thisfraction were dissolved in 100 gm of dimethyl sulfoxide containing 57 mlof allyl chloride. The temperature of the resulting mixture wasincreased to 60° C. It was maintained at this temperature, withagitation, for a period of 8 hours at which time the allyl dimethylamine was essentially completely converted to diallyl dimethyl ammoniumchloride. The diallyl dimethyl ammonium chloride product was soluble inthe dimethyl sulfoxide. It could effectively be polymerized in theorganic solution using conventional techniques.

EXAMPLE 2

Into a suitably sized reaction vessel equipped with reflux means(maintained at -45° C.), addition funnels, stirrer, heating and coolingmeans and thermometer was added 1836 ml of a 40 weight percent solutionof dimethyl amine in water and 200 ml toluene. During this addition, thereaction vessel was maintained at 25° C. Subsequently, 682 ml of 50weight percent aqueous solution of sodium hydroxide was added dropwiseto the dimethyl amine/water/toluene mixture over a period of threehours. Simultaneous with the addition of the sodium hydroxide was added1077 ml of allyl chloride. During the addition of sodium hydroxide andallyl chloride, the reaction mixture was maintained at a temperature of25° C. Following complete addition of allyl chloride and sodiumhydroxide, the molar ratio of dimethyl amine:allyl chloride:sodiumhydroxide contained in the reaction vessel was 1.115:1:1. After completeaddition of sodium hydroxide and allyl chloride, the temperature of thereaction mixture was slowly increased to 55° C. This temperature wasmaintained for an additional three hours. The flask was then cooled to20° C. At this time, the toluene phase which contained the allyldimethyl amine reaction product formed a top layer whereas the aqueousphase which contained the sodium chloride formed a bottom layer. Theyield, based on the amounts of allyl chloride fed to the reactor, wasover 80 percent. The allyl dimethyl amine product can be quaternizedusing any of the foregoing techniques in Example 1 (B-G) to form diallyldimethyl ammonium chloride, as a solid or an aqueous or organic liquidsolution, at a surprisingly high purity.

EXAMPLE 3

To a suitably sized and equipped reaction vessel containing 200 gm ofn-hexane was added 200 gm of a 50 weight percent aqueous solution ofmorpholine. The resulting mixture was vigorously agitated. Subsequently,82 gm of allyl chloride was added dropwise to the reaction mixture overa 3 hour period. Simultaneously, 82 gm of a 50 weight percent solutionof sodium hydroxide in water were added within 3 hours. During thisaddition, the temperature was maintained at 30° C. The vessel was heatedto 60° C. for an additional 5 hours, then cooled to room temperature.The organic phase was separated and fractionated. The fraction boilingat 30 mm Hg and 60° C. contains pure N-allyl morpholine, which can bequaternized using conventional techniques.

We claim:
 1. A method for preparing a solid quaternary diallyl dialkylammonium compound by sequentially reacting a secondary amine with anallyl halide in a liquid reaction diluent and the presence of an alkalimetal or alkaline earth metal hydroxide or carbonate and subsequentlyreacting the thus prepared allyl dialkyl amine with additional amountsof an allyl halide in a liquid reaction diluent to from a quaternarydiallyl dialkyl ammonium salt wherein the reaction of the secondaryamine and allyl halide is conducted in a two-phase liquid reactiondiluent comprising an aqueous liquid and a water-immiscible organicsolvent and at least a portion of the organic liquid phase is separatedfor further reaction of the allyl dialkyl amine contained by thisorganic phase to prepare the quaternary diallyl dialkyl ammoniumcompound in an organic liquid quaternization reaction diluent.
 2. Themethod of claim 1 wherein said allyl halide is added directly to theseparated organic phase to quaternize the allyl dialkyl amine.
 3. Themethod of claim 1 wherein said allyl dialkyl amine is recovered from theseparated organic liquid phase and redissolved in the same or differentorganic liquid quaternization reaction diluent for subsequentquaternization to the diallyl dialkyl ammonium compound.
 4. The methodof claim 3 wherein said organic liquid quaternization reaction diluentis an aromatic hydrocarbon, al aliphatic hydrocarbon having six or morecarbon atoms, a lower ketone or a compatible mixture thereof and from 2to 50 volumes of the organic liquid are employed for each volume of theamine to be quaternized.
 5. The method of claim 4 wherein said organicliquid quaternization reaction diluent is a lower ketone or an aromatichydrocarbon, the allyl halide is allyl chloride and is employed in atleast a stoichiometric amount based on the amount of allyl dialkyl amineto be quaternization reaction is conducted at a temperature from 20° to60° C.
 6. The method of claim 5 wherein said organic liquidquaternization reaction diluent is acetone.